Diphenethylbenzene tetracarboxylic acid derivatives



United States Patent US. Cl. 260-515 2 Claims ABSTRACT OF THE DISCLOSURECertain derivatives of diphenethylbenzene-u,a.,/3,B- tetracarboxylicacid are valuable as synthetic resin intermediates to prepareplasticizers, 'fiame-proofing agents, gear oil additives, hightemperature grease additives, fun icid s and bacteroiostats.

The present application is a division of our copending application, Ser.No. 373,065, filed June 5, 1964, now US. Patent 3,293,278, granted Dec.20, 1966.

This invention relates to new chemical compounds and particularly toderivatives of diphenethylbenzene tetracarboxylic acids. These compoundswhich exhibit utility as synthetic resin intermediates are characterizedby the following structural formula:

Ym Zn Yrn ital T 7 at at 41:0 l

OH OHOH Y is a monovalent substituent selected from the group consistingof alkyl, aryl and aryloxy radicals, alkoxy radicals containing from 1to 18 carbon atoms, nitro radicals, halogens and secondary and tertiaryamino radicals,

Z is a monovalent substituent selected from the group consisting ofmethyl radicals and halogens,

m is a cardinal number from O to inclusive, and

n is a cardinal number from O to 4 inclusive.

Tetracyanodiphenethylbenzene, the parent compound of the presentinvention, can be prepared by the condensation of abenzenediacetonitrile with a benzaldehyde to formdibenzylidenebenzenediacetonitrile followed by cyanation of thedibenzylidenebenzenediacetonitrile. The condensation and cyanation canbe conducted in a onestep operation, or the introduction of theadditional nitrile groups can be deferred until the condensation iscomplete. The tetracyanodiphenethylbenzene thus obtained is thenhydrolyzed to the tetracarboxylic acid of diphenethylbenzene.

As indicated above, benzaldehyde can be used in the preparation of thepresent invention. However, in the preparation of compounds havingsubstituents on the terminal benzene rings, it is preferred to usesubstituted benzaldehydes rather than to add the substituents after thecondensation reaction. Specific examples of substituted benzaldehydesthat can be employed include methylbenzaldehydes, ethylbenzaldehydes,propylbenzaldehydes, butylbenzaldehydes, decylbenzaldehydes,doclecylbenzaldehydes, octylbenzaldehydes, methoxybenzaldehydes,ethoxybenzaldehydes, propoxybenzaldehydes, butoxybenzaldehydes,nonoxybenzaldehydes, undecoxybenzaldehydes, octadecoxybenzaldehydes,phenylbenzaldehydes, tolylbenzaldehydes, phenoxybenzaldehydes,toloxybenzaldehydes, nitrobenzaldehydes, chlorobenzaldehydes, fluoroicebenzadehydes, bromobenzaldehydes, iodobenzaldehydes,nitrohalobenzaldehydes, alkylhalobenzaldehydes, alkoxyhalobenzaldehydes,aroxyhalobenzaldehydes, alkylnitrobenzaldehydes,alkylnitrohalobenzaldehydes and the like.

The substituents on the benzaldehyde nucleus can vary in number from onethrough five, be like or unlike, and members of the groups indicatedhereinbefore.

The benzenediacetonitrile to be condensed with the benzaldehyde may beortho, meta or para, substituted or unsubstituted. Suitablebenzenediacetonitrile include mono-, di-, tri-, andtetra-methylbenzenediacetonitriles, mono-, di-, triandtetra-chlorobenzenediacetonitriles, mono-, di-, triandtetra-fiuorobenzenediacetonitriles, mono-, di, triandtetra-bromobenzenediacetonitriles, and mono-, di-, triandtetra-i0dobenzenediacetonitriles. Mixed ha1obenzenediacetonitriles andmethylhalobenzenediacetonitriles may also be employed. Examples ofsuitable benzenediacetonitriles of these groups include chlorofiuoro-,chlorobromo-, chloroiodo-, fluorobromo-, fluoroiodo-, bromoch1oro-,brornoiodo-, chlorohromoiodo-, methylchloro-, methylfiuoro-, methyliodo,methylbromobenzenediacetonitriles and the like.

The invention will be further clarified by reference to the followingdetailed descriptions of the preparation of compounds encompassedthereby. Unless otherwise specified, all proportions in these examplesand throughout the specification are expressed in parts by weight.

Example l.p-Diphenethylbenzene-u,ot,B,fi-tetracarboxylic acid In a 1liter beaker equipped with a vigorous stirrer there were placed about 53g. of redistilled benzaldehyde, about 39 g. of p-benzenediacetonitrile,and 325 ml. of ethanol. The mixture was warmed to dissolve thereactants, then allowed to cool to 45 C. Sodium ethoxide was prepared byadding 1.2 g. of sodium to 25 ml. of ethanol, and this alkali solutionwas added dropwise to the stirred reaction mixture. After 7 ml. of thealkali had been added, a precipitate formed rapidly which transformedthe reaction mixture to a thick paste. Stirring and addition of alkaliwere stopped, the mixture was cooled to room temperature, and theprecipitate was collected by filtration. After washing with a mixture ofWater and ethanol, the material is recrystallized from acetonitrile.33.2 g. of the product was transferred to a 3 liter flask equipped witha stirrer, a reflux condenser, and a dropping funnel. There is added 1liter of triethylamine and 1 liter of methanol. A solution of 24.5 g. ofsodium cyanide in 40 ml. of warm water was then added rapidly to thestirred, boiling nitrile suspension, followed by a solution of 11.5 ml.of acetic acid in 90 ml. of methanol to hold the color to a pale redhue. (In the absence of added acetic acid, the mixture approaches a deepfuchsia.) After 1.5 hours an additional 5 ml. of acetic acid was added,and the very pale pink solid,a,a.,/3,fi-tetracyano-p-diphenethylbenzene, was filtered from the hotliquors, washed twice with 200 ml. portions of methanol and twice with200 ml. portions of water.

To a mixture of 50 g. of one, 8,B'-tetracyano-p-diphenethylbenzene and112.5 ml. of water there is added 956 ml. of concentrated sulfuric acid.By swirling and warming to 80-90 C. the nitrile was dissolved. Thesolution was allowed to stand at room temperature for 3 hours and thenit was diluted with about 540 ml. of water. This mixture was held at for8 hours, and then allowed to cool. The solid which separated wascollected, washed, and dissolved in dilute ammonium hydroxide. This darksolution was decolorized by passing through a column of decolorizingcarbon. The pale yellow percolate was heated and stirred with 10 ml. ofacetic acid. Then 40 ml. of concentrated hydrochloric acid was added.The white precipitate which formed was collected,

3 washed thoroughly with water, and dried. This material melted Wellover 300 C.

Analysis.-Calcd. for C H O (462.44): C, 67.53; H, 4.80; neut. eq.,115.61. Found: C, 65.74; H, 5.53; 5.00; neut. eq., 124.

Evaporation of the mother liquors allowed recovery of an additional 0.4of tan solid with the same neutral equivalent.

Similarly, other diphenethylbenzene tetracarboxylic acids can beprepared by the hydrolysis of tetracyanodiphenethylbenzenes having thedesired substituents on one or more of their benzene rings. Suitabletetracyanodiphenethylbenzenes that can be thus hydrolyzed include, forinstance, those obtained in accordance with Examples 2 through 22 Whereequivalent amounts of benzaldehydes (II) and benzene diacetonitriles(III) are reacted to yield various a,043 33-tetracyanodiphenethylbenzenes (I).

Examples 2 (I) a,a,6,6- tetracyano o diphenethylbenzene (II)benzaldehyde (III) o-benzenediacetonitrile (I)a,a,6,fi-tetracyano-m-diphenethylbenzene (II) benzaldehyde (III)m-benzenediacetonitrile (I) 4,4 dimethyl a,a',fi,15' tetracyano pdiphenethylbenzene (II) d-methylbenzaldehyde (III)p-benzenediacetonitrile (I) 2,2 dimethyl a,a,B,B tetraeyano pdiphenethylbenzene (II) 2-methy1benzaldehyde (III)p-benzenediacetonitrile (I) 3,3 dimethyl a,rz',fi,' tetraeyano pdiphenthylbenzene (II) 3 methylbenzaldehyde (III)p-benzenediacetonitrile (I) 4,4"-dioctadecyl 01,06,116tetracyano-p-diphenethylbenzene (II) 4-0etadeeylbenzaldehyde (III)p-benzenediacetonjtrile (1) 4,4 dimethoxy nee/,Bfi' tetracyano pdiphenethylbenzene (II) 4-methoxybenzaldehyde (III)p-benzenediacetonitrile (1) 2,2 dimethoxy a,a,;8,fl tetracyano pdiphenethylbenzene (II) 2-methoxybenzaldehyde (III)p-benzenediacetonitrile (I) 3,3"-dimethoxy a,a,fl,fl tetracyano pdiphenethylbenzene (II) 3-methoxybanzaldehyde (III)p-benzenediacetonitrile (I) 4,4 dioctadecoxy a,a,fi,fi' tetracyano pdlpllonethylbenzene (II) 4-octadeeoxybenzaldehyde (III)p-benzenediacetonitrile (I) 4,4 diphenyl ,a,5, 5 tetracyano pdiphenethylbenzene (II) 4-phenylbenzaldehyde (III)p-benzenediacetonitrile (I) 4,4 diphenoxy a,a,5,5 tetracyano p diphenethylbenzene (II) 4-phenoxybenza1dehyde (III) p-benzenediacetonitrile (I)3,3 dinitro a,z, 8,fl tetracyano p diphenethylbenzene (II)m-nitrobenzaldehyde (III) p-benzenediacetonitrile (1) 3,3 dichloroa,a,5,fi tetracyano p diphenethylbenzene (II) m-chlorobenzaldehyde (III)p-benzenediacetonitrile (I) 2 methyl a,a',B,B' tetracyano pdiphenethylbenzene (II) benzaldehyde (III) 2 methyl pbenzenediacetonitrile (I) 2- chloro a,a,,fi,fltetracyano pdiphenethylbenzene (II) benzaldehyde (III) 2 chloro pbenzenediacetonitrile (I) 2,3,5,6 tetraehloro a,a,/3, 8 tetracyano pdiphenethylbenzene (II) benzaldehyde (III) 2,3 5.6 -tetrachlorobenzene1,4 diacetonitrile (I) 3,4,3,4-tetran1ethoxy-a,a,B,B-tetracyano-p-diphenethylbenzene (II)veratraldehyde (3,4 djmethoxybenzaldehyde) (III) p-benzenediacetonitrile(I) 2 nitro a,a,5,fl tetracyano p diphenethylbenzene (II) benzaldehyde(III) Z-nitro-p-benzenediacctonitrile Examples 21 (I) 3,3 (linitro 4.4dimethyl a,a,fi,6 tetracyano m diphenethylbenzene (II)3-nitro-4m1ethylbenzaldehyde (III) m-benzenediaeetonitrile 22 (I) 3,3,3"trinitro a,a,B,B-tetraeyano p diphenethyrbenzene (II)m-nitrobenzaldehyde (III) 2-nitro-p-benzenediacetonitrile It isself-evident that the various substituted tetracarboxylic acids .thusobtained can be utilized in the preparation of the corresponding esters,anhydrides, imides, carboxamides and mixed ester-carboxamides.

The compounds produced in accordance with the present invention arecrystalline compounds of moderate molecular weight. They are insolublein water, but readily soluble in a variety of commercially availablesolvents. They are of particular value as resin intermediates, and alsoas (intermediates in the preparation of) plasticizers, flame proofingagents, gear oil additives, high temperature grease additives,fungicides and in numerous other industrial applications. In addition anumber of the compounds under consideration exhibit bacteriostaticproperties. For example, p-diphenethylbenzene-zx,o'$3.5- tetracarboxylicacid possesses inherent antibacterial activity against Salmonellatyphosa. These products are particularly valuable since they present aseries of compounds in which the melting point can be varied while thechemical characteristics are maintained substantially constant. Highmelting products are obtained by using the para form of benzenediacetonitrile as the starting material, whereas the ortho and metabenzene diacetonitriles yield lower melting products.

The tetracarboxylic acids of the present invention can be esterifiedwith alcohols, such as glycerine, pentaerythritol, sorbitol, mannitol,ethylene glycol and the like in the preparation of polyester and alkylresins having high softening points and film-forming properties.

Numerous modifications and additional compounds will readily suggestthemselves to those skilled in the art. Thus, while the invention hasbeen described with particular reference to specific embodiments, it isto be understood that it is not to be limited thereto but is to beconstrued broadly and restricted'solely by the scope of the appendedclaims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A diphenethylbenzene-o ',fi, 8'-tetracarboxylic acid of the formulawherein Y is a monovalent substituent selected from the group consistingof phenyl, tolyl, phenoxy, tolyloxy. alkyl or alkoxy each having up to18 carbon atoms, nitro and halogen; Z is methyl or halogen; m is acardinal number from 0 to 5 inclusive; and n is a cardinal number from 0to 4 inclusive.

2. p-Diphenethylbenzene-a,a,/3,[i"-tetracarboxylic acid.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner M. G. BERGER, AssistantExaminer US. Cl. X.R. 260520 mg UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3, 68,957 te September 23, 1969 Inventor-(s)Ronald H. Wile It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 5, Line 30, after "it", insert has been found particularlyadvantageous to employ a mixture of the two. It

SIGRED AND SEALED FEB 2 4 1970 sun Anew nmm z. saaunm, .m. AmmingOfficer Oomisaioner of Patents

